EP0971982B1 - Corps moules thermoplastiques comportant des segments de differentes rigidites - Google Patents

Corps moules thermoplastiques comportant des segments de differentes rigidites Download PDF

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Publication number
EP0971982B1
EP0971982B1 EP19980919232 EP98919232A EP0971982B1 EP 0971982 B1 EP0971982 B1 EP 0971982B1 EP 19980919232 EP19980919232 EP 19980919232 EP 98919232 A EP98919232 A EP 98919232A EP 0971982 B1 EP0971982 B1 EP 0971982B1
Authority
EP
European Patent Office
Prior art keywords
component
weight
molding
shaped article
polyamide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19980919232
Other languages
German (de)
English (en)
Other versions
EP0971982A1 (fr
Inventor
Alexander Glück
Walter Götz
Volker Lohrbächer
Graham Edmund Mc Kee
Mark VÖLKEL
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0971982A1 publication Critical patent/EP0971982A1/fr
Application granted granted Critical
Publication of EP0971982B1 publication Critical patent/EP0971982B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31728—Next to second layer of polyamide
    • Y10T428/31732—At least one layer is nylon type

Definitions

  • cooling liquid lines can be extrusion blow molded, combined with 3D tube manipulation become.
  • a disadvantage of these molded parts is the use of layers made of polyolefin components with comparatively low heat resistance.
  • the object of the invention is therefore to provide thermoplastic molded parts with alternating Provide hard / soft segments, with the soft segments in addition to high flexibility, especially high chemical resistance and heat resistance and also good adhesion added to a hard segment consisting essentially of polyamide is. It is also an object of the invention to use molded parts with different segments Rigidity from components that are connected to one another over a large area to provide, each of the components having a high thermoforming and Resistance to heat aging, high long-term use temperature, high chemical resistance, especially high resistance to oil, fuel and Coolants, as well as a high tensile or burst pressure resistance.
  • the molding compositions A contain 40 to 100, preferably 70, as component A1 to 100, particularly preferably 85 to 100 wt .-% of a thermoplastic Polyamids, coplyamids or their blends.
  • Partly crystalline polyamides are preferably used, preferably PA 6, PA 66, PA 6T / 6, PA 6 / 6T, PA 6T / 6I, PA 6T / 66, PA 6T / 6I / 66 PA 66 / 6T (Copolycondensates from hexamethylenediamine, adipic acid, caprolactam and Iso- or terephthalic acid) and PA 46. Mixtures of different Polyamides are used. Polyamides are particularly preferred 66 and polyamide 6, especially polyamide 6 used.
  • component A2 alone or in a mixture with the called fibrous reinforcing materials, mineral fillers such as Wollastonite, kaolin, quartz, mica or calcium carbonate are present.
  • the molding composition A can contain up to 20% by weight impact modifiers contain.
  • Impact modifiers are with reactive groups grafted polyolefins and are known per se. Suitable impact modifiers are for example in US 4,174,358, column 6, line 21 to column 7, line 26.
  • UV stabilizers are substituted resorcinols, sterically hindered Phenols, salicylates, benzotriazoles and benzophenones, which are generally can be used in amounts of up to 2% by weight.
  • a flame retardant for example, red or black Phosphorus or a phosphorus-containing compound in amounts of 3 to 10 Use% by weight.
  • the preferred flame retardant is elemental phosphorus, especially in combination with glass fiber reinforced molding compounds.
  • the molding composition B contains 20 to 79.9, preferably 20 to 70, particularly preferably 25 to 55, in particular 30 to 45% by weight at least a thermoplastic polyamide, copolyamide or their blends. It the polyamides can be used, which also as component A1 in the molding compound A may be included. Are particularly preferred here also polyamide 66 and polyamide 6, especially polyamide 6.
  • the molding composition B can contain up to 30, preferably up to 10 % By weight of other additives and processing aids. It the additives and processing aids can be used, the can also be contained in the molding composition A as component A4.
  • olefinically unsaturated monomers B23 with a polyamide reactive group are particularly suitable acrylic acid, methacrylic acid, maleic acid, Maleic anhydride, fumaric acid and glycidyl methacrylate, in particular Acrylic acid or methacrylic acid.
  • the graft shell is made in emulsion as e.g. in DE-B 12 60 135, DE-A 32 27 555, DE-A 31 49 357 and DE-A 34 14 118 is described.
  • the moldings are made from molding compounds A and B, whose tensile modulus of elasticity is at least differ by a factor of 2.
  • the molding compositions contain A and B as components A1 and B1 the same polyamide.
  • extruders e.g. Single screw or Twin screw extruders or other conventional plasticizers like Brabender mills or Banbury mills.
  • the graft copolymerization product obtained in aqueous dispersion can, for example by spray drying, before mixing be dried completely and as a powdery polymer be mixed with the other components. But it can also how described in DE-A 33 13 919, the aqueous polymer dispersion used become.
  • the polyamide in the mixing device is preferably used first plasticized. When mixing the polyamide melt with the The polymer dispersion then evaporates the water and the rubber particles are distributed evenly in the melt.
  • the production of the molded articles from the molding compositions A and B can be done according to known methods take place, for example by injection molding, extrusion or Extrusion blow molding.
  • the molded articles can be produced, for example, by injection molding. Molding compositions A or B can be applied to a solidified section molded or extruded from the other molding compound.
  • the molded articles can also be produced in two-component injection molding by simultaneous injection with both molding compositions A and B, preferably from opposite ends of the injection mold.
  • the production of molded bodies in injection molding is preferably carried out from Molding compositions A and B, the polyamide components A1 and B1 polyamides with a viscosity number of 140 to 185 included.
  • the molding compositions A and B are particularly advantageous for the production of Hollow moldings used.
  • the production of hollow moldings from different Molding compositions A and B are generally carried out by coextrusion the molding compositions A and B, the shaping nozzle of at least two different extruders.
  • a tube is extruded which has both molding compositions A and B.
  • the extruded hose the desired molded body itself - for example a straight tube - or be a preform from which through further process steps the molded body is produced.
  • a hose is extruded that distributes one over the wall thickness Sequence of layers of the same or different thickness from each has one of the molding compositions A or B, the layer thickness and composition remains constant over the entire length of the hose.
  • the production of the hollow molded articles or preforms is more advantageous by sequential coextrusion, i.e. H. with alternating material flows.
  • This can be done in such a way that the shaping nozzle alternates from each of the extruders, d. H. alternating with molding compound A only or the molding compound B is loaded.
  • a tube is extruded, which has an alternating composition over its entire length Has segments of only one of the molding compounds A or B.
  • the Switching from one extruder to the other can be sudden or take place continuously within a limited time interval.
  • Preforms or moldings can also be extruded, the more have only two layers, the sequence of layers of can be any inside out, and the thickness of each layer can vary.
  • the molded body can be made up of three Layers with the sequence A-B-A or B-A-B are present.
  • the moldings can also have segments with different numbers of layers.
  • the moldings according to the invention preferably have two layers.
  • the shaping can also take place in such a way that the preform inflated first and then the mold is closed. Thereby are generally obtained hollow molded body with a circumferential pinch seam.
  • the production of hollow moldings with a complicated geometry can also by combining blow molding and so-called 3D extrusion.
  • a tube is extruded and deformed according to the Molded contours inserted in the open half of the tool.
  • the insertion the hose can be moved, for example, by moving the open blow mold under the extruder, by moving the extruder over the open one Blow molding or by manipulation of the extruded tube using a Gripping arm done.
  • the blow mold is closed and the hose inflated.
  • the extruded tube can also be sucked into the blow mold and be inflated.
  • Process for 3D extrusion or tube manipulation are known to the person skilled in the art. Hollow moldings are becoming more complicated Preserve geometry without all-round pinch seam.
  • the molding composition B has, despite its possibly high proportion of olefin polymer the properties typical of polyamides such as high Heat resistance and good solvent resistance. This Properties are consequently also in the soft segments (with a high Share of molding compound B). Also the tensile strength of the component B comparatively high. Draw the moldings according to the invention therefore has a high burst pressure resistance over its entire length out.
  • VZ 300 (Ultramid KR 4465 G4 from BASF AG)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Materials For Medical Uses (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (12)

  1. Corps moulés constitués de
    a) 5 à 95% en poids d'une masse de moulage A à base de
    a1) 40 à 100% en poids d'au moins un polyamide, copolyamide thermoplastique, ou leurs mélanges, en tant que composant A1,
    a2) 0 à 60% en poids de charges et / ou d'agents de renforcement en tant que composant A2,
    a3) 0 à 20% en poids de modificateurs de la résistance au choc en tant que composant A3,
    a4) 0 à 30% en poids d'autres additifs et adjuvants de traitement en tant que composant A4,
    la somme des quantités des composants A1 et éventuellement A2 à A4 totalisant 100% en poids,
    b) 5 à 95% en poids d'une masse de moulage B constituée de
    b1) 20 à 79,9% en poids d'au moins un polyamide, copolyamide thermoplastique, ou leurs mélanges, comme composant B1,
    b2) 20,1 à 80% en poids d'au moins un polymère réticulé à élasticité de caoutchouc en tant que composant B2 et
    b3) 0 à 30% en poids d'autres additifs et adjuvants de traitement en tant que composant B3,
    la somme des quantités des composants B1, B2 et éventuellement B3 totalisant 100% en poids,
    et des segments constitués des masses thermoplastiques A et B étant liés ensemble par leur surface dans les corps moulés.
  2. Corps moulés selon la revendication 1, où la masse de moulage A présente une ou plusieurs des caractéristiques ci-après:
    le composant A1 contient du polyamide 6 et / ou 66,
    le composant A2 est constitué de fibres de verre,
    le composant A4 contient des stabilisants à la chaleur,
    l'indice de viscosité du composant A1 est de 130 à 500,
    le module d'élasticité à la traction de la masse de moulage A est > 2000 MPa.
  3. Corps moulés selon la revendication 1 ou 2, où la masse de moulage B présente une ou plusieurs des caractéristiques ci-après:
    le composant B1 contient du polyamide 6 et / ou 66,
    le composant B3 contient des stabilisants à la chaleur,
    le module d'élasticité à la traction de la masse de moulage B est de 50 à 1500 MPa,
    la température de ramollissement Vicat (méthode B) de la masse de moulage B est > 180°C.
  4. Corps moulés selon l'une des revendications 1 à 3, caractérisés en ce que les composants B2 sont des copolymères préparés par polymérisation en émulsion, à partir de:
    b21) 50 à 97,9% en poids d'au moins un monomère oléfiniquement insaturé, de préférence un alkylester en C1-8 de l'acide acrylique, en particulier de l'acrylate de n-butyle et / ou de l'acrylate d'éthylhexyle en tant que composant B21,
    b22) 2 à 50% en poids d'au moins un monomère réticulant polyfonctionnel en tant que composant b22 et
    b23) 0,1 à 10% en poids d'au moins un monomère oléfiniquement insaturé comportant un groupe réactif vis-à-vis du polyamide, de préférence de l'acide acrylique, de l'acide méthacrylique, de l'acide maléique, de l'anhydride maléique, de l'acide fumarique et / ou du méthacrylate de glycidyle, en particulier de l'acide acrylique ou de l'acide méthacrylique, en tant que composant B23,
    la somme des quantités des composants B21, B22 et B23 totalisant 100% en poids, avec une ou plusieurs des caractéristiques suivantes:
    B2 est un polymère à noyau / gaine,
    les groupes réactifs se trouvent uniquement dans la gaine,
    la température de transition vitreuse du noyau est < 0°C,
    la taille de particules est de 0,01 à 10 µm.
  5. Corps moulés selon l'une des revendications 1 à 4 présentant au moins l'une des caractéristiques suivantes:
    les modules d'élasticité en traction des masses de moulage A et B diffèrent d'au moins un facteur 2,
    les masses de moulage A et B contiennent le même polyamide.
  6. Corps moulé selon l'une des revendications 1 à 5, caractérisé en ce que le corps moulé est un corps creux.
  7. Corps moulé selon la revendication 6, sous la forme de tuyau d'amenée d'air ou de liquide de refroidissement pour véhicules automobiles.
  8. Corps moulé selon la revendication 6 ou 7, où la paroi du corps moulé creux constitue au moins en partie, de l'extérieur vers l'intérieur, une succession de couches constituées des masses de moulage A et B, et présentant de l'extérieur vers l'intérieur la séquence A - B et / ou B - A.
  9. Corps moulés selon l'une des revendications 1 à 8, préparés par moulage par injection, extrusion ou extrusion-soufflage.
  10. Procédé de préparation de corps moulés constitués des masses de moulage A et B, telles que définies dans les revendications 1 à 5, par
    moulage par injection, auquel cas les composants A1 et B1 présentent un indice de viscosité de 140 à 185, ou
    extrusion, auquel cas les composants A1 et B1 présentent un indice de viscosité de190 à 285, ou
    extrusion-soufflage, auquel cas les composants A1 et B1 présentent un indice de viscosité de 250 à 400.
  11. Utilisation des masses de moulage A et / ou B, telles que définies dans les revendications 1 à 5, pour la production de corps moulés, tels que définis dans les revendications 1 à 9.
  12. Utilisation de corps moulés selon l'une des revendications 1 à 9 dans le domaine de l'automobile.
EP19980919232 1997-04-11 1998-04-07 Corps moules thermoplastiques comportant des segments de differentes rigidites Expired - Lifetime EP0971982B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19715120A DE19715120A1 (de) 1997-04-11 1997-04-11 Thermoplastische Formkörper mit Segmenten unterschiedlicher Steifigkeit
DE19715120 1997-04-11
PCT/EP1998/002022 WO1998046681A1 (fr) 1997-04-11 1998-04-07 Corps moules thermoplastiques comportant des segments de differentes rigidites

Publications (2)

Publication Number Publication Date
EP0971982A1 EP0971982A1 (fr) 2000-01-19
EP0971982B1 true EP0971982B1 (fr) 2003-06-18

Family

ID=7826208

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19980919232 Expired - Lifetime EP0971982B1 (fr) 1997-04-11 1998-04-07 Corps moules thermoplastiques comportant des segments de differentes rigidites

Country Status (7)

Country Link
US (1) US6254949B1 (fr)
EP (1) EP0971982B1 (fr)
JP (1) JP2001521567A (fr)
AT (1) ATE243236T1 (fr)
DE (2) DE19715120A1 (fr)
ES (1) ES2202844T3 (fr)
WO (1) WO1998046681A1 (fr)

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KR100633377B1 (ko) * 1998-12-10 2006-10-16 솔루티아인코포레이티드 비-할로겐화 폴리아미드 조성물
ATE314599T1 (de) * 1999-10-29 2006-01-15 Piolax Inc Gewelltes harzrohr
US20030114831A1 (en) * 2001-12-14 2003-06-19 Scimed Life Systems, Inc. Catheter having improved curve retention and method of manufacture
US20050103332A1 (en) * 2003-11-17 2005-05-19 Bruce Gingles Airway exchange catheter
US20050136272A1 (en) * 2003-12-23 2005-06-23 Vanrheenen Paul Gloss reducing polymer composition
US7601285B2 (en) * 2003-12-31 2009-10-13 Boston Scientific Scimed, Inc. Medical device with varying physical properties and method for forming same
DE102004036179A1 (de) * 2004-07-26 2006-03-23 Degussa Ag Kühlmittelleitung
DE102005046087B3 (de) * 2005-09-26 2007-04-05 Carcoustics Tech Center Gmbh Schallisolierende Unterbodenverkleidung für Kraftfahrzeuge
US9707898B1 (en) * 2016-07-11 2017-07-18 Ford Global Technologies, Llc Extruded multi-layer molded running board
US20180290515A1 (en) * 2017-04-11 2018-10-11 Ford Motor Company Multi-layer blow molded extrusion
EP3670184A1 (fr) * 2018-12-20 2020-06-24 EMS-Patent AG Conduite de transport de fluide et son utilisation
DE102019111458A1 (de) * 2019-05-03 2020-11-05 Kuhne Anlagenbau Gmbh Verfahren zur Herstellung einer mehrschichtigen Verbundfolie, mehrschichtige Verbundfolie und deren Verwendung

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JP3476037B2 (ja) * 1995-04-21 2003-12-10 矢崎総業株式会社 ポリアミド樹脂組成物

Also Published As

Publication number Publication date
EP0971982A1 (fr) 2000-01-19
ATE243236T1 (de) 2003-07-15
ES2202844T3 (es) 2004-04-01
WO1998046681A1 (fr) 1998-10-22
DE59808759D1 (de) 2003-07-24
DE19715120A1 (de) 1998-10-15
US6254949B1 (en) 2001-07-03
JP2001521567A (ja) 2001-11-06

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